JP5399636B2 - Dinaphthylethylene derivatives, methods for their synthesis, films made from dinaphthylethylene derivatives and organic electroluminescent diodes comprising the films. - Google Patents

Description

The present invention relates to a dinaphthylethylene derivative, a synthesis method thereof, a film made from the dinaphthylethylene derivative, an organic electroluminescence diode (hereinafter referred to as OLED) using the film, a thin film containing OLED, and a dinaphthylethylene derivative. The present invention relates to a method for manufacturing the OLED used.

OLED begins in the 60s. In 1963, p.pone et al. First discovered the luminescence phenomenon of single-crystal anthracene. However, since the driving voltage was as high as 400V, this phenomenon did not attract people's attention. In 1987, Kodak's C.I. W. By TANG et al., Alq ₃ and HTM-2 were vapor-deposited to produce an amorphous film as an organic light emitting device. And the drive voltage was as low as 20V or less. For this reason, OLED attracted much attention all over the world (Patent Document 1). OLED has advantages such as high brightness, wide viewing angle, fast photoelectric response speed, low driving voltage, low power consumption, full color, high contrast, light weight, and easy manufacture. For this reason, it is widely used for panel light emitting diodes such as flat panel displays and light pans.

The OLED is composed of two electrodes and at least one organic thin film sandwiched between the two electrodes. This organic thin film is made from electroluminescence. In general, electroluminescence having a D-π-X structure (D is a donor) has high fluorescence efficiency. In addition, the emission wavelength of the OLED depends on X. Here, X is Cheng C.I. H. In the case of a strong donor such as the diaminoanthracene derivative (Non-Patent Document 1) synthesized by J. et al., The produced OLED usually emits green light. X is Chen C.I. T. T. et al. Synthesized coumarin derivatives (Non-patent Document 2), Lin J. T. T. et al. Anthracylallylamine (Non-patent Document 3), Huang C. et al. With a weak donor such as carbazolyloxadiazole synthesized by G (Non-patent Document 4), the produced OLED emits blue light. Furthermore, OLED emits red light on a substrate in which X includes a strong acceptor such as an NPAFN derivative (Non-patent Document 5). On the other hand, π-crosslinking is also important. If the π-donating property is too strong, the emission wavelength of the OLED becomes long, which adversely affects the color of the OLED. Conversely, if the π donating property is too weak, the current efficiency of the OLED is deteriorated. For example, when an OLED is synthesized with a diphenylethylene group, there is a problem that current efficiency and lifetime are adversely affected (Patent Document 2).
US Pat. No. 4,356,429 People's Republic of China Patent 1388800A Chem Mater, 2002, 14: 3958 Org Lett, 2003, 5: 1261 Chem Mater, 2002, 14: 3860 Chem Commun, 2003, 2708 Chem Commun, 2003, 2632

  One of the objects of the present invention is to provide a novel organic electroluminescent compound. The compound can produce an OLED with high color purity, high fluorescence, and high brightness. Further, the compound can be easily synthesized and can be easily formed into a thin film. Furthermore, the compound can produce an OLED in which the emission wavelength varies depending on the type of substituent and the position of the substituent in the compound. Another object of the present invention is to provide a method for producing the electroluminescent compound.

  The compound of the present invention is a compound represented by the following formula (I).

(I)

(In formula (I), R _{1 to} R ₁₆ are each a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, an alkylthio group, an aryl group, a heterocyclic aromatic group, and a condensed aromatic group. An aromatic group, a condensed heterocyclic aromatic group, or an arylamino group, and at least one of R _{1 to} R ₁₄ is not a hydrogen atom)

In the formula (I), R _{1 to} R ₁₆ are a hydrogen atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, C2-C30 substituted or unsubstituted amino group, C1-C30 substituted or unsubstituted alkylthio group, C6-C20 substituted or unsubstituted aryl group, C6-C20 substituted or unsubstituted condensation Aromatic group, substituted or unsubstituted heterocyclic aromatic group having 4 to 20 carbon atoms, substituted or unsubstituted condensed heterocyclic aromatic group having 4 to 20 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms And at least one of R _{1 to} R ₁₄ may not be a hydrogen atom.

In the formula (I), R _{1 to} R ₁₆ are each a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a methoxy group, an ethoxy group, an isopropoxy group, 3 Primary butoxy group, N, N-dimethylamino group, N, N-diethylamino group, methylthio group, ethylthio group, isopropylthio group, tertiary butylthio group, phenyl group, biphenyl group, naphthyl group, anthryl group, pyrenyl group, Fluorenyl group, naphthacenyl group, pyridyl group, quinolyl group, benzothiophenyl group, benzofuranyl group, indolyl group, benzimidazolyl group, benzothiazole group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N- Phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group Group, Carbazolyl group, pyrrolyl group, thiophenyl group, furanyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyridyl group, quinolyl group, isoquinolyl group, carbazolyl group, phenanthridinyl group, benzothiothiophenyl group, Benzofuranyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, thiadiazole group, oxadiazolyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, azobenzothiophenyl group, indolyl group, thiaindolyl group, thiisoindolyl group, thiaindazolyl group And a compound selected from the group consisting of pyrazoloquinolyl groups, and at least one of R _{1 to} R ₁₄ may not be a hydrogen atom.

  The compound of the present invention may be a compound represented by the following formula (II).

(II)

(In the formula (II), Ar ₁ and Ar ₂ each represent a hydrogen atom, a substituted or unsubstituted aryl group, an aryl vinyl group, a condensed aromatic group, a vinyl substituted condensed aromatic group, an arylamino group, and at least one nitrogen atom. A condensed ring containing, a heterocyclic ring containing at least one nitrogen atom)

In the formula (II), Ar ₁ and Ar ₂ are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl vinyl group having 8 to 40 carbon atoms, and 6 to 6 carbon atoms. 30 substituted or unsubstituted condensed aromatic groups, vinyl substituted condensed aromatic groups having 14 to 60 carbon atoms, arylamino groups having 6 to 30 carbon atoms, condensed rings having 6 to 30 carbon atoms and containing at least one nitrogen atom or May be a compound having 6 to 30 carbon atoms and a heterocyclic ring containing at least one nitrogen atom.

Further, in the formula (II), Ar ₁ and Ar ₂ are each a phenyl group, biphenyl group, naphthyl group, anthryl group, pyrenyl group, fluorenyl group, naphthacenyl group, phenyl vinyl group, naphthyl vinyl group, anthryl vinyl group, Fluorenyl vinyl group, phenanthryl vinyl group, biphenyl vinyl group, diphenyl vinyl group, phenyl naphthyl vinyl group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N-phenyl-N- ( 1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, substituted or The compound may be an unsubstituted quinoxalinyl group or a carbazolyl group.

  The compound of the present invention may be a compound represented by the following formula (III).

(III)

(In Formula (III), X and Y are a methylene group, an aromatic 5-membered or 6-membered ring having 1 to 3 heteroatoms and 4 to 20 carbon atoms, 1 to 3 heteroatoms and 6 to 20 carbon atoms, respectively. And at least one of X and Y is not a methylene group, and Ar ₃ and Ar ₄ are each a hydrogen atom, a fluorine atom, a carbonyl group, a cyano group, or an acyloxy group. A vinylidene group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted amino group having 2 to 30 carbon atoms, 30 substituted or unsubstituted alkylthio groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, condensed aromatic groups having 6 to 20 carbon atoms, and arylamine groups having 6 to 30 carbon atoms)

In the formula (III), X and Y are a methylene group, a pyrrolyl group, a thiophenyl group, a furanyl group, a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a carbazolyl group, Selected from the group consisting of phenanthridinyl group, benzothiophenyl group, benzofuranyl group, benzoimidazolyl group, benzooxazolyl group, benzothiazolyl group, oxadiazolyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, indolyl group, X and At least one of Y is not a methylene group. In addition, Ar ₃ and Ar ₄ are hydrogen atom, fluorine atom, carbonyl group, cyano group, acyloxy group, vinylidene group, methyl group, ethyl group, isopropyl group, tertiary butyl group, methoxy group, ethoxy group, isopropoxy, respectively. Group, tertiary butoxy group, N, N-dimethylamino group, N, N-diethylamino group, methylthio group, ethylthio group, isopropylthio group, tertiary butylthio group, phenyl group, biphenyl group, naphthyl group, anthryl group, pyrenyl Group, fluorenyl group, naphthacenyl group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) ) From amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, carbazolyl group, p-carbazolylphenyl group, pN, N-diphenylaminophenyl group Than the group It may be a compound selected.

Further, in the formula (III), X is from the following formulas (IV) to (XV), Y is from the following formulas (XVI) to (XXV), and Ar ₃ is the following formula (XXXVI) to formulas. From (XXXXII), Ar ₄ may be a compound selected from the following formulas (XXXXIII) to (XXXXVI).

(IV)

(V)

(VI)

(VII)

(VIII)

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV)

(XV)

(XVI)

(XVII)

(XVIII)

(XIX)

(XX)

(XXI)

(XXII)

(XXIII)

(XXIV)

(XXV)

(XXVI)

(XXVII)

(XXVIII)

(XXIX)

(XXX)

(XXXI)

(XXXII)

(XXXIII)

(XXXIV)

(XXXV)

(XXXVI)

(XXXVII)

(XXXVIII)

(XXXIX)

(XXXX)

(XXXXI)

(XXXXII)

(XXXXIII)

(XXXXIV)

(XXXXV)

(XXXXVI)

(XXXXVII)

(XXXXVIII)

(XXXXIX)

(XXXX)

(XXXXXXI)

(XXXXII)

(XXXXIII)

(XXXXIV)

(XXXXV)

(XXXXVI)

  The compound of the present invention may be a compound selected from the group consisting of the following formulas (C1) to (C141).

C1

C2

C3

C4

C5

C6

C7

C8

C9

C10

C11

C12

C13

C14

C15

C16

C17

C18

C19

C20

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33

C34

C35

C36

C37

C38

C39

C40

C41

C42

C43

C44

C45

C46

C47

C48

C49

C50

C51

C52

C53

C54

C55

C56

C57

C58

C59

C60

C61

C62

C63

C64

C65

C66

C67

C68

C69

C70

C71

C72

C73

C74

C75

C76

C77

C78

C79

C80

C81

C82

C83

C84

C85

C86

C87

C88

C89

C90

C91

C92

C93

C94

C95

C96

C97

C98

C99

C100

C101

C102

C103

C104

C105

C106

C107

C108

C109

C110

C111

C112

C113

C114

C115

C116

C117

C118

C119

C120

C121

C122

C123

C124

C125

C126

C127

C128

C129

C130

C131

C132

C133

C134

C135

C136

C137

C138

C139

C140

C141

  The method for synthesizing the compound of the present invention is a method for synthesizing a compound having one of the following steps a), b), c) and d).

  a) In the presence of an inert solvent containing titanium (IV) chloride and zinc, the structural formula (Ia) and the structural formula (Ib) are reacted in an inert gas atmosphere. A step of appropriately inserting a substituent into the place.

(Ia)

(Ib)

(In the structural formula (1-a) and the structural formula (1-b), R _{1 to} R ₁₄ are each defined as any one of R _{1 to} R ₁₄ described above)

b) reacting structural formula (Ia ′) with structural formula (Ib ′) in the presence of an inert solvent containing titanium (IV) chloride and zinc under an inert gas atmosphere; A step of appropriately inserting a substituent into a required place.

(I-a ')

(1-b ')

(In the structural formula (1-a ′) and the structural formula (1-b ′), R _{1 to} R ₁₆ are each defined as any one of R _{1 to} R ₁₆ described above)

c) From the structural formula (Ia), the structural formula (Ia ′), the structural formula (Ib), and the structural formula (Ib ′) in the presence of an inert solvent having an alkali. A step of reacting one of the compounds selected from the group and the compound represented by the structural formula (Ic), and inserting a substituent appropriately at a required position.

(I c)

(In the structural formula (Ic), R _{1 to} R ₇ are each defined as any one of R _{1 to} R ₇ described above, and R ₁₇ is a straight chain or moiety having 1 to 6 carbon atoms. A branched alkyl group)

  d) In the presence of an inert solvent having an alkali metal or alkaline earth metal alcoholate and iodine, a compound represented by the structural formula (Id) and a compound represented by the structural formula (Ie) The process of making it react and inserting a substituent into a required place suitably.

(Id)

(Ie)

(In the structural formula, R _{1 to} R ₁₄ are defined by any of R _{1 to} R ₁₄ described above)

  The substance used at the beginning of the method for synthesizing the above formula (I) is well known to those skilled in the art, the method for synthesizing the substance is well known to those skilled in the art, or the synthesis method is shown below. Very similar to one of the examples.

  The thin film of the present invention is a thin film useful for an organic electroluminescence diode, and is a thin film made of any of the compounds described above and deposited on a substrate.

This thin film is synthesized from a dinaphthylethylene derivative represented by the above formula (I) (R _1-16 is as defined above), and is suitable for OLED production by a known method such as evaporation or sputtering. It is deposited on the substrate.

  The organic electroluminescent diode of the present invention is an organic electroluminescent diode including the thin film.

The dinaphthylethyl derivative represented by the formula (I) (R _1-16 is as defined above) can be used for the production of OLEDs. This dinaphthylethyl derivative can be used as a host or a dye of the light emitting layer, and can also be used as an electron transport layer or a hole blocking layer.

  The present invention will be described in more detail. However, the following examples are for illustrative purposes only and are not intended to limit the technical scope of the present invention. Also, unless otherwise specified, starting materials are commercially available.

(Preparation of starting material)
Production Method of Arylboronic Acid: A method for synthesizing 4-biphenylboric acid will be described using FIG. FIG. 1 is a reaction formula for explaining a method for synthesizing 4-biphenylboric acid. Magnesium (0.85 g, 0.035 mol), ethane bromide (0.5 ml), and anhydrous THF (15 ml) were placed in a dry three-necked flask (100 ml) attached to a reflux condenser, and a magnetic stirrer was placed under an argon atmosphere. Was used to prepare a mixture. 4-Bromobiphenyl (5.83 g, 0.025 mol) was dissolved in anhydrous THF (20 ml) and a portion of the aqueous solution (1.0 ml) was added to the mixture. The reaction was performed by heating, and the remainder of the 4-bromobiphenyl solution prepared earlier was added over 10 minutes. Stirring was performed under reflux for 2 hours. The Grignard reactant was cooled to −78 ° C. with an alcohol-liquid nitrogen bath, and newly distilled trimethylboric acid (3.25 ml, 0.03 mol) was slowly added dropwise to the reaction to obtain a mixture. The cooling bath was removed and the mixture was stirred overnight at room temperature. The mixture was slowly added to hydrochloric acid (10%, 20 ml) and further stirred for 30 minutes. The mixture was extracted with ether (30 ml, 3 times). The organic layer was collected, washed until the washing solution became neutral, and dried over anhydrous magnesium sulfate. The organic phase was filtered under reduced pressure, and the solvent was removed to obtain a stick-like substance. This material was treated with petroleum ether (60 ml) to give a slightly yellowish white powder. This white powder was 4-biphenylboric acid (3.2 g).

  Other aryl-substituted boric acids and aryl-substituted boric acids could be synthesized in the same manner.

  Method for Producing Bromo-Substituted Naphthalene Derivative: A method for producing a bromo-substituted naphthalene derivative will be described with reference to FIG. FIG. 2 is a reaction formula for explaining a synthesis method of 6-bromo-2-naphthaldehyde.

Synthesis method of 6-bromo-2-naphthylmethanol: Lithium aluminum hydride (40 g, 1.05 mol) and anhydrous THF (500 ml) were added to a three-necked flask (5 L) cooled in an ice bath under nitrogen filling. . To this suspension, a solution of methyl-6-bromo-2-naphthate (141 g, 0.534 mol) dissolved in anhydrous THF (1200 ml) was slowly added dropwise with a funnel. The cooling bath was removed and the mixture was allowed to react by stirring for an additional 2 hours. The mixture was cooled again in an ice bath, and methanol (150 ml) was carefully added dropwise so as not to generate gas. The mixture was stirred for an additional 30 minutes and then acidified with hydrochloric acid to about pH 4.0. The resulting salt was removed by vacuum filtration and the filtrate was concentrated and poured into deionized water (2 L). The precipitate was collected with a suction filter, washed with deionized water, added with a small amount of ethanol, and vacuum-dried to obtain 6-bromo-2-naphthylmethanol (95.4 g).

  Synthesis of 2-bromo-6- (bromomethyl) naphthalene: 6-bromo-2-naphthylmethanol (47.4 g, 0.20 mol) and chloroform (600 ml) were added to a three-necked flask (2 L). The mixture was cooled to −35 ° C. with an ethanol-liquid nitrogen bath. To the suspension, phosphorus (III) bromide (28.6 ml, 0.603 mol) was slowly added dropwise over 25 minutes. The cooling bath was removed and stirring was continued for an additional 2.5 hours at room temperature. The mixture was cooled again, and methanol (250 ml) was slowly added dropwise and absorbed into potassium hydroxide to release hydrogen bromide quickly. The mixture was warmed to room temperature and the precipitate was collected by vacuum filtration. The obtained residue was washed with ethanol and dried to give 2-bromo-6 (bromomethyl) naphthalene (35 g) as a white solid.

  Synthesis of dimethyl (6-bromo-2-naphthyl) methylphosphonic acid: In a three-necked flask (250 ml), 2-bromo-6 (bromomethyl) naphthalene (35.0 g, 0.117 mol) and trimethylphosphoric acid (18 ml,. 152 mol) was added. The reaction was heated to 150 ° C. and stirred with a magnetic stirrer for 3 hours. Excess trimethyl phosphate was removed by distillation under reduced pressure. The residue was cooled at room temperature to give a white solid. This solid was pulverized, washed with petroleum ether, collected by vacuum filtration, and finally dried in vacuo to give dimethyl (6-bromo-2-naphthyl) methylphosphonic acid (43 g) as a white solid.

  Synthesis of 6-bromo-2-naphthaldehyde: 6-bromo-2-naphthylmethanol (40.0 g, 0.170 mol) and dichloromethane (1.6 L) were added to a three-necked flask (250 ml) under a nitrogen atmosphere. Were mixed using a magnetic stirrer to obtain a transparent solution. To this solution was added chromium pyrinidium chloride salt (40.0 g, 0.186 mol), the mixture reacted and immediately turned black. Thereafter, stirring was continued for 1 hour. The mixture was passed through a short silica gel column and eluted with dichloromethane. The filtrate was dried using anhydrous magnesium sulfate and filtered under reduced pressure. When the solvent was removed, a light brown solid was obtained, and this salt was recrystallized using 50% ethanol to obtain 6-bromo-2-naphthaldehyde (31 g) as a white solid.

  Example 1 A method for synthesizing Compound C1 will be described with reference to FIG. FIG. 3 is a reaction formula for explaining a synthesis method of compound C1.

  Synthesis of intermediate C1-1: 2-bromothiophene (16.30 g, 100 mmol), phenylboronic acid (15.24 g, 125 mmol), palladium (II) acetate (0.22 g, 1 mmol), triphenyl phosphate (0 .53 g, 2 mmol), potassium carbonate (34.50 g, 250 mmol) and toluene (250 ml) were added to a three-necked flask (500 ml), and the mixture was stirred using a magnetic stirrer under a nitrogen atmosphere. The resulting mixture was heated to reflux for 4 hours, cooled to room temperature, poured onto silica gel (15 ml) and eluted with petroleum ethanol. The solvent was removed by distillation under reduced pressure to obtain C1-1 (14.2 g).

  Synthesis of intermediate C1-2: 2-phenylthiophene (8.01 g, 50 mmol) and anhydrous THF (100 ml) were added to a three-necked flask (250 ml), and the mixture was stirred using a magnetic stirrer under an argon atmosphere. The resulting mixture was cooled to −78 ° C. with an ethanol-liquid nitrogen bath. A solution prepared by dissolving n-butyllithium in n-hexane (2.5 M, 24 ml, 60.0 mmol) was added dropwise to this mixture. Subsequently, stirring was continued at −78 ° C. for 1.5 hours. Distilled trimethylboric acid (3.25 ml, 0.03 mol) was slowly added dropwise (8.5 ml, 75.6 mmol). The cooling bath was removed and stirring was continued overnight at room temperature. Hydrochloric acid (10%, 20 ml) was added. The organic layer was separated, dried over anhydrous magnesium sulfate and separated. The solvent was removed by vacuum distillation. Potassium ether was added to the residue, and the precipitate was removed by filtration under reduced pressure to obtain C1-2 (9.1 g), a light green salt.

  Synthesis of intermediate C1-3: In the same manner as C1-2 except that C1-2 and 6-bromo-2-naphthaldehyde were used instead of phenylboronic acid and 2-bromothiophene, respectively, C1-3 (4.2 g) was obtained.

  Synthesis of Compound C1: Zinc powder (3.9 g, 60 mmol) and anhydrous THF (30 ml) were added to a three-necked flask (100 ml) and stirred using a magnetic stirrer under an argon atmosphere. The resulting mixture was cooled to −10 ° C. using a cooling bath. To this cooled mixture, titanium tetrachloride (6.6 ml, 30 mmol) was added dropwise over 30 minutes through a dry dropping funnel. The resulting mixture was warmed under reflux for 2 hours and then cooled. A cooled mixture was added dropwise over 10 minutes to a solution of C1-3 (3.14 g, 10 mmol) in anhydrous THF (30 ml) and the resulting mixture was warmed under reflux overnight. The reaction product thus obtained was cooled to room temperature and filtered under reduced pressure. The residue was washed with THF (5 ml) to obtain a greenish yellow solid. Then, it suspended with deionized water, the supernatant liquid was filtered, and it vacuum-dried and obtained C1 (2.8g).

Compound C1 has an MS (m / e) of 596, and as a result of component analysis, the experimental measurement ■ is C: 84.51%, H: 4.78%, S: 10.71%, and the theoretical value of C ₄₈ H ₂₈ S ₂ is C: 84.53%, H: 4.73%, S: 10.75%.

  Example 2 A method for synthesizing compound C12 will be described with reference to FIG. FIG. 4 is a reaction formula for explaining a synthesis method of compound C12.

Synthesis of intermediate C12-1: 2-bromoindole (7.00 g, 35.7 mmol), copper acetate (0.8 g, 4.8 mmol), 2,4-dimethylpyridine (2 ml) and myristic acid (1.104 g) , 4.8 mmol), phenylboric acid (5.8 g, 48 mmol) and toluene (100 ml) were added to a three-necked flask (250 ml), and the mixture was stirred with a magnetic stirrer for 24 hours under an oxygen atmosphere. The mixture was stripped of black material with a short silica gel column and the filtrate was evaporated under reduced pressure. The residue was crystallized from petroleum ether to obtain C12-1 (5.8 g) as white crystals.

  Synthesis of Intermediates C12-2, C12-3, and C12: In the same manner as in Example 1, C12 (2.4 g) as a yellow solid was finally obtained.

Compound C MS (m / e) is 662, the result of component analysis, experimental measurements ■ is C: 90.60%, H: 5.17 %, N: and 4.23% theoretical value of C ₅₀ H ₃₄ N ₂ is C: 90.59%, H: 5.13%, N: 4.22%.

  Example 3 A method for synthesizing compound C19 will be described with reference to FIG. FIG. 5 is a reaction formula for explaining a synthesis method of compound C19.

  Synthesis of intermediate C19-1: 2-bromo-5-iodothiophene (28.9 g, 100 mmol), N-phenyl-2-naphthamine (24.1 g, 110 mmol) and copper iodide (1.9 g, 10 mmol) Anhydrous potassium phosphate (53 g, 200 mmol) and ortho-xylene (250 ml) were added to a three-necked flask (500 ml), and the mixture was heated to reflux for 24 hours under nitrogen protection while stirring with a magnetic stirrer. The mixture was cooled to room temperature and filtered under reduced pressure. The solvent was removed from the filtrate by vacuum distillation. Next, it refine | purified using the silica gel column, and wash | cleaned with petroleum ether, and obtained C19-1 (19.6g).

  Subsequent operations were performed in the same manner as in Example 1 to obtain C19 (1.2 g).

The MS (m / e) of Compound C is 879, and as a result of component analysis, the experimental measurement values are C: 84.71%, H: 4.78%, S: 7.31%, N: 3.20%, C ₆₂ H ₄₂ S theoretical value of ₂ N ₂ is C: 84.70%, H: 4.82 %, S: 7.29, N: was 3.19%.

  Example 4 A method for synthesizing compound C32 will be described with reference to FIG. FIG. 6 is a reaction formula for explaining a synthesis method of compound C32.

  Synthesis of C32-3: Synthesis was performed in the same manner as the synthesis method of C1-3 in Example 1 except that N-methyl-2-bromopyrrole was used instead of 2-bromothiophene.

  Synthesis of C32-4: C32-3 (6.22 g, 0.020 mol), dimethyl (6-bromo-2-naphthyl) methylphosphonate (7.24 g, 0.022 mol) and sodium hydroxide (55 wt%, 1.28 g, 0.030 mol) and anhydrous THF (25 ml) were added to a three-necked flask (100 ml) under a nitrogen atmosphere. The resulting mixture was heated to reflux for 15 hours with stirring using a magnetic stirrer. The mixture was cooled to room temperature and methanol (2 ml) was carefully added. The mixture was poured into water (50 ml), filtered under reduced pressure, and the residue was recrystallized from ethyl acetate to give C32-4 (6.1 g).

  Synthesis of compound C32: C32-4 (5.14 g, 0.01 mol), tertiary butoxy sodium (2.87 g, 0.030 mol), N-phenyl-2-naphthaamine (2.4 g, 0.011 mol) and acetic acid (II) Palladium (0.1 g, 0.5 mmol), triphenylphosphine (0.26 g, 1 mmol) and anhydrous toluene (60 ml) were added to a three-necked flask (50 ml), and a magnetic stirrer was used under an argon flow. And stirred. The mixture was heated to reflux overnight. The mixture was cooled to room temperature, filtered through a short silica gel column and eluted with toluene to remove black material and give a sticky material. The sticky substance was cooled, solidified, pulverized, dissolved in absolute ethanol, and filtered to obtain yellow powder C32 (5.52 g).

Compound C has an MS (m / e) of 652, and as a result of component analysis, experimental measurement values are C: 90.00%, H: 5.49%, N: 4.23%, and the theoretical value of C ₄₉ H ₃₆ N ₂ is C: 90.15%, H: 5.56%, N: 4.29%.

  Example 5 A method for synthesizing compound C34 will be described with reference to FIG. FIG. 7 is a reaction formula for explaining a synthesis method of compound C34.

  Synthesis of intermediate C34-1: C34-1 (13 g) was obtained in the same manner as C32-4 (Example 4) except that diphenyl (6-bromo-2-naphthyl) methylphosphonic acid was replaced with benzophenone.

  Synthesis of intermediate C34-2: C34-1 (7.71 g, 0.020 mol), tetramethylethylenediamine (5.3 ml, 0.040 mol) and anhydrous THF (60 ml) were added to a three-necked flask (250 ml). The mixture was stirred under an argon flow using a magnetic stirrer. The mixture was cooled to −78 ° C. with an ethanol-liquid nitrogen bath. After mixing, a solution in which n-butyllithium was dissolved in n-hexane (2.5 M, 16 ml, 0.040 mol) was slowly added dropwise to obtain a deep blue solution, and then stirring was continued at −78 ° C. for 1 hour. . A solution of dimethylformamide (15.1 ml, 0.2 mol) dissolved in THF (15 ml) was slowly added dropwise. The cooling bath was removed and hydrochloric acid (10%, 55 ml) was added and mixed at room temperature. The mixed purified product was stirred for 1 hour. The mixture was extracted with ethyl acetate. The mixed organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the solid obtained was recrystallized using ethanol-ethyl acetate (Vol / Vol = 2: 1) to obtain a light yellow solid. C34-2 (6.7 g) was obtained.

  Synthesis of Compound C34: C34 (6.7 g) as a yellow solid was obtained in the same manner as C1-3 (Example 1) except that C34-2 was used instead of C1-2.

Compound C has an MS (m / e) of 616. As a result of component analysis, the experimental measurement values are C: 89.50%, H: 5.28%, S: 5.18%, and the theoretical value of C ₄₆ H ₃₂ is C: 89.57%, H: 5.23%, S: 5.20%.

  Example 6 A method for synthesizing compound C53 will be described with reference to FIG. FIG. 8 is a reaction formula for explaining a synthesis method of compound C53.

  Compound C53 (3.8 g) was obtained in the same manner as in Example 1 except that 4-biphenylboric acid was used instead of C1-2.

The MS (m / e) of Compound C is 584. As a result of component analysis, the experimental measurement values are C: 94.41%, H: 5.58%, and the theoretical value of C ₄₆ H ₃₂ is C: 94.48%, H: It was 5.52%.

  Example 7 A method for synthesizing compound C55 shown in FIG. 9 will be described. FIG. 9 is a structural formula showing the compound C55.

  A yellow powdery C55 was obtained in the same manner as in Example 6 except that 4- (2 ', 2'-diphenylvinyl) phenylboric acid was used instead of 4-biphenylboric acid.

The MS (m / e) of Compound C is 788. As a result of component analysis, experimental measurement values are C: 94.41%, H: 5.60%, and the theoretical value of C ₄₆ H ₃₂ is C: 94.38%, H: It was 5.62%.

  Example 8 A method for synthesizing compound C60 will be described with reference to FIG. FIG. 10 is a reaction formula for explaining a synthesis method of compound C60.

  Synthesis of intermediate C60-1: Pale yellow powder in the same manner as the synthesis method of C53-1 (Example 6) except that 3,5-diphenylphenylboric acid was used instead of 4-biphenylboric acid C60-1 (2.6 g) was obtained.

  Synthesis of Compound C60: C60 (1.8 g) as a yellow solid was obtained in the same manner as the synthesis method of C53 except that C60-1 was used instead of C53-1.

The MS (m / e) of Compound C is 736. As a result of component analysis, the experimental measurement values are C: 94.50%, H: 5.44%, and the theoretical value of C ₅₈ H ₄₀ is C: 94.53%, H: It was 5.47%.

Example 9 A method for synthesizing compound C67 will be described with reference to FIG. FIG. 11 is a reaction formula for explaining a synthesis method of compound C67.

  In the same manner as C32 (Example 4), C67 (3.3 g) as a yellow solid was obtained.

Compound C has an MS (m / e) of 675. As a result of component analysis, the experimental measurement values are C: 92.45%, H: 5.50%, N: 2.00%. The theoretical value of C ₅₂ H ₃₇ N is C : 92.41%, H: 5.52%, N: 2.07%.

Example 10 A method for synthesizing compound C68 will be described with reference to FIG. FIG. 12 is a reaction formula for explaining a synthesis method of compound C68.

  Synthesis of intermediate C68-1: In the same manner as dimethyl (6-bromo-2-naphthyl) methylphosphonic acid except that 4-bromomethylbiphenyl was used instead of 2-bromo-6- (bromomethyl) naphthalene Synthesized to obtain C68-1 (4.6 g) as a white solid.

  Synthesis of intermediate C68-2: C34-1 except that C68-1 and 6-bromo-2-naphthaldehyde were used instead of benzophenone and dimethyl (6-bromo-2-naphthyl) methylsulfonic acid Synthesis was carried out in the same manner as in Example 5 to obtain C68-2 (4.2 g) as a white solid.

  Synthesis of intermediate C68-3: C68-3 (2) which is a pale yellow solid was synthesized in the same manner as C34-2 (Example 5) except that C68-2 was used instead of C34-1 .2 g) was obtained.

  Synthesis of intermediate C68-4: Synthesis was performed in the same manner as C34-3 (Example 5) except that C68-3 was used instead of C34-2, and C68-4 (2 0.5 g) was obtained.

  Synthesis of Compound C68: Compound C68 was synthesized in the same manner as C32 (Example 4) except that diphenylamine and C68-4 were used instead of 2-naphthylphenylamine and C32-4, respectively. (2.3 g) was obtained.

Compound C has an MS (m / e) of 625, and as a result of component analysis, the experimental measurement values are C: 92.10%, H: 5.60%, N: 2.22%, and the theoretical value of C ₄₈ H ₃₅ N is C : 92.12%, H: 5.64%, N: 2.24%.

  Example 11 A method for synthesizing compound C75 will be described with reference to FIG. FIG. 13 is a reaction formula for explaining a synthesis method of compound C75.

  Synthesis of intermediate C75-1: Three-necked 6-bromo-2-naphthylaldehyde (20.0 g, 0.085 mol), glycol (40 ml, 0.715 mol), iodine (0.24 g, 0.9 mmol) and toluene (20 ml) In addition to the flask (100 ml), the mixture was stirred using a magnetic stirrer under a nitrogen flow. The mixture was heated to reflux. After 6 hours, anhydrous sodium carbonate (21.2 g, 0.2 mol) was added, and the reaction product was refluxed overnight. The mixture was cooled at room temperature, poured into deionized water (200 ml) and vacuum filtered. The residue was recrystallized with chloroform, and the crystal was vacuum-dried to obtain C75-1 (16.8 g) as a yellow solid.

  Synthesis of intermediates C75-2 and C75-3: C75-1 (4.17 g, 0.015 mol), carbazole (2.76 g, 0.016 mol), copper iodide (2.86 g, 0.016 mol) and anhydrous potassium carbonate (4.17 g, 0.030 mol), 18-uraun-6 (0.08 g, 0.002 mol) and DMPU (45 ml) were added to a three-necked flask (100 ml) under an argon flow. The mixture was refluxed for 4 hours. The mixture was cooled and kept stirring at room temperature overnight. Deionized water (50 ml) was added and the resulting solid was filtered under reduced pressure. The residue was washed with deionized water and dissolved in acetone. The resulting mixture was further stirred for 8 hours. The precipitate was filtered under reduced pressure and recrystallized with ethyl acetate to obtain C75-3 (1.9 g) as a pale yellow solid.

  Synthesis of intermediate C75-4: C75-4 (2) which is a pale yellow solid was synthesized in the same manner as C34-3 (Example 5) except that C75-3 was used instead of C34-2. .36 g) was obtained.

  Synthesis of compound C75: Synthesis was performed in the same manner as in C32 (Example 4) except that C75-4 was used instead of C32-4 to obtain C75 (2.65 g) as a yellow solid.

The MS (m / e) of Compound C is 662, and as a result of component analysis, the experimental measurement values are C: 90.59%, H: 5.20%, N: 2.20%, and the theoretical value of C ₅₀ H ₃₄ N ₂ is C: 90.60%, H: 5.17%, N: 2.23%.

  Example 12 A method for synthesizing compound C80 will be described with reference to FIG. FIG. 14 is a reaction formula for explaining a synthesis method of compound C80.

  Synthesis of intermediate C80-1: C80 (2.55 g) as a yellow solid was synthesized in the same manner as C34-4 (Example 4) except that C60-1 was used instead of C34-2. Got.

  Synthesis of Compound C80: Synthesis was performed in the same manner as in C68 (Example 10) except that C80-1 was used instead of C68-4 to obtain C80 (2.34 g) as a yellow solid.

Compound C has an MS (m / e) of 675. As a result of component analysis, the experimental measurement values are C: 92.40%, H: 5.55%, N: 2.07%, and the theoretical value of C ₅₂ H ₃₇ N is C : 92.41%, H: 5.52%, N: 2.07%.

  Example 13 A method for synthesizing compound C81 will be described with reference to FIG. FIG. 15 is a structural formula of Compound C81.

  Synthesis was carried out in the same manner as C80 (Example 12) except that 4-biphenylaniline was used instead of dimethylamine to obtain C81 (1.6 g) as a yellow solid.

Compound C has an MS (m / e) of 751, and as a result of component analysis, the experimental measurement values are C: 92.66%, H: 5.50%, N: 1.90%, and the theoretical value of C ₅₈ H ₄₁ N is C : 92.64%, H: 5.50%, N: 1.86%.

  (Example 14): The synthesis method of compound C82 is demonstrated using FIG. FIG. 16 is a reaction formula for explaining a synthesis method of compound C82.

  Synthesis of intermediate C82-1: C82-1 (9.7 g), which is a white solid, was synthesized in the same manner as C34-1 (Example 5) except that 1-benzylnaphthalene was used instead of benzophenone. )

  Synthesis of Intermediate C82-2: Synthesis was performed in the same manner as in C34-2 (Example 5) except that C82-1 was used instead of C34-1, and C82-2 (4. 28 g) was obtained.

  Synthesis of Compound C82: Synthesis was performed in the same manner as C53 (Example 6) except that C82-2 was used instead of C53-1, to obtain C82 (5.6 g) as a yellow solid.

The MS (m / e) of Compound C is 736. As a result of component analysis, the experimental measurement values are C: 94.51%, H: 5.44%, and the theoretical value of C ₅₈ H ₄₀ is C: 94.53%, H: It was 5.47%.

  (Example 15): The synthesis method of compound C98 is demonstrated using FIG. FIG. 17 is a reaction formula for explaining a synthesis method of compound C98.

  Synthesis of intermediate C98-1: Synthesis was carried out in the same manner as C34-1 (Example 5) except that fluorenone was used instead of benzophenone to obtain C98-1 (8.5 g) as a yellow solid. It was.

  Synthesis of Intermediate C98-2: Anhydrous THF (20 ml), a small piece of magnesium (0.72 g, 0.030 mol) and a small amount of element were placed in a three-necked flask (250 ml), and a magnetic stirrer was used under argon flow. Stir with. The reaction was started by heating, a solution of C98-1 (5.74 g, 0.015 mol) in anhydrous THF (100 ml) was added, and the mixture was heated to reflux for 20 hours. The reaction proceeded even after the addition reaction was completed, and a precipitate formed on the wall of the flask due to the Grignard reaction. After refluxing to stop the exothermic reaction, the mixture was stirred with a stirrer and slowly warmed to reflux for 4 hours.

  The mixture was slowly cooled until the reflux was complete. Then, triethyl orthoformate (2.22 g, 0.015 mol) was added dropwise to the mixture over 5 minutes, and the mixed reaction was heated to reflux for 6 hours. The mixture was cooled in a cooling bath and cooled hydrochloric acid (10%, 7.5 ml) was slowly added dropwise. The organic layer was extracted and concentrated under reduced pressure. To the residue was added sulfuric acid (25%, 7.5 ml) and the reaction product was heated to reflux for 12 hours.

  The mixture was then cooled with a cooling bath. The acid supernatant was removed and the residue was washed twice with water. This residue was dissolved in benzene (7.5 ml) in the same flask. Then, water (11 ml) and sodium sulfite (9 g) were added to the mixed reaction product. The mixture was vigorously stirred overnight. The mixture was filtered and washed with a Butcher funnel with benzene (5 ml).

  The residue was divided and returned to the same flask (50 ml). The sodium bicarbonate suspension was added slowly with stirring until there was no sign of any further dissolution of the compound. The mixture was stirred for an additional 2 hours. Sodium bicarbonate was added as necessary to make the solution alkaline. The crude aldehyde was collected by vacuum filtration and the residue was washed with water and dried. The crude aldehyde was recrystallized with ethanol / anhydrous ethanol to obtain C98-2 (2.0 g) as a pale yellow solid.

  Synthesis of intermediate C98-3: C98-3 (2) which was synthesized in the same manner as C32-4 (Example 4) except that C98-2 was used instead of C32-3. .75 g) was obtained.

  Synthesis of Compound C98: Synthesis was performed in the same manner as in C32 (Example 4) except that C98-3 was used instead of C32-4 to obtain C98 as a yellow solid.

Compound C has an MS (m / e) of 673. As a result of component analysis, the experimental measurement values are C: 92.66%, H: 5.18%, N: 2.08%, and the theoretical value of C ₅₂ H ₃₅ N is C : 92.69%, H: 5.24%, N: 2.08%.

(Example 16): The synthesis method of compound C101 is demonstrated using FIG. FIG. 18 is a reaction formula for explaining a synthesis method of compound C101.

  Synthesis of intermediate C101-1: The same as C1-1 (Example 1) except that 3-bromocarbazole and 3-methylphenylboric acid were used instead of 2-bromothiophenyl and phenylboric acid, respectively. By the method, C101-1 (3.7 g) was obtained as a white solid.

  Synthesis of Intermediates C101-2 and C101-3: Pale yellow solids were synthesized in the same manner as C75-2 and C75-3 (Example 11), respectively, except that C101-1 was used instead of carbazole. C101-3 (1.77 g) was obtained.

  Synthesis of Compound C101: Synthesis was performed in the same manner as C60 (Example 8) except that C101-3 was used instead of C60-1, to obtain C101 (2.98 g) as a yellow solid.

Compound C has an MS (m / e) of 790. As a result of component analysis, the experimental measurement values are C: 91.10%, H: 5.35%, N: 3.54%, and the theoretical value of C ₆₀ H ₄₂ N ₂ is C: 91.11%, H: 5.35%, N: 3.54%.

  Example 17 A method for synthesizing compound 103 will be described with reference to FIG. FIG. 19 is a structural formula of the compound C103.

  Synthesis of Compound C103: Synthesis was performed in the same manner as in Example 6 except that 4- (4′-biphenyl) phenylboric acid was used instead of 4-biphenylboric acid, and C103 (1. 6 g) was obtained.

The MS (m / e) of Compound C is 736. As a result of component analysis, the experimental measurement values are C: 94.42%, H: 5.57%, and the theoretical value of C ₅₈ H ₄₀ is C: 94.53%, H: It was 5.47%.

  Example 18: A method for synthesizing compound C107 will be described with reference to FIG. FIG. 20 is a structural formula of the compound C107.

  Synthesis of Compound C107: Synthesis was performed in the same manner as in Example 6 except that 2-perynylboric acid was used instead of 4-biphenylboric acid to obtain C107 (1.10 g) as a yellow solid.

Compound C has an MS (m / e) of 780. As a result of component analysis, the experimental measurement values are C: C: 95.32%, H: 4.60%, and the theoretical value of C ₆₂ H ₃₆ is C: 95.35%. H: 4.65%.

  (Example 19): The synthesis method of compound C113 is demonstrated using FIG. FIG. 21 is a structural formula of compound C113.

  Synthesis of compound C113: 4- (2 ′, 2′-diphenylvinyl) phenylboric acid and 6-bromo-5-methyl-2-naphtho instead of 4-biphenylboric acid and 6-bromo-2-naphthaldehyde The compound was synthesized in the same manner as in Example 6 except that each aldehyde was used to obtain C113 (1.8 g) as a yellow solid.

The MS (m / e) of Compound C is 816. As a result of component analysis, the experimental measurement values are C: 94.10%, H: 5.92%, and the theoretical value of C ₆₄ H ₄₈ is C: 94.08%, H: It was 5.92%.

  Example 20 A method for synthesizing compound C116 will be described with reference to FIG. FIG. 22 is a structural formula of the compound C116.

  Instead of 4- (2 ', 2'-diphenylvinyl) phenylboric acid, 6-bromo-2-methylnaphthalene and 6-bromo-2-naphthaldehyde, 2-naphthylboric acid and 6-bromo-7- (N , N-dimethylamino) -2-methylnaphthalene and 6-bromo-7- (N, N-dimethylamino) -2-naphthylaldehyde were used in the same manner as in Example 19, respectively. C116 (1.2 g) was obtained as a yellow solid.

Compound C has an MS (m / e) of 746. As a result of component analysis, the experimental measurement values are C: 90.00%, H: 6.21%, N: 3.74%, and the theoretical value of C ₅₆ H ₄₆ N ₂ is C: 90.04%, H: 6.21%, N: 3.75%.

(Example 21): The synthesis method of compound C120 is demonstrated using FIG. FIG. 23 is a reaction formula for explaining a synthesis method of compound C120.

  Synthesis of intermediate C120-1: Synthesis was performed in the same manner as C53-1 (Example 6) except that 6-bromo-2-methylnaphthalene was used instead of 6-bromo-2-naphthaldehyde. C120-1 (48 g) was obtained as a pale yellow solid.

  Synthesis of intermediate C120-2: C120-1 (29.4 g, 0.1 mol) and anhydrous THF (400 ml) were placed in a three-necked flask (1000 ml) and stirred using a magnetic stirrer. An anhydrous THF (400 ml) solution in which N-bromosuccinide (17.8 g) was dissolved was added dropwise to the mixture. The resulting mixture was further stirred at room temperature for 12 hours. The mixture was poured into sodium carbonate suspension (300 ml) and extracted with ethanol acetate (200 ml, 3 times). The organic layer was collected, washed with deionized water until the washing solution was neutral, and dried over anhydrous magnesium sulfate. The organic layer was filtered and the solvent was removed to obtain C120-2 (24.5 g) as a white solid.

  Synthesis of intermediate C120-3: Synthesis was performed in the same manner as 2-bromo-6- (bromomethyl) naphthalene to obtain C120-3 (38.6 g) as a white powder.

  Synthesis of Compound C120: Similar to C32-4 (Example 4) except that C120-3 and C120-4 were used instead of 2-bromo-6- (bromomethyl) naphthalene and C32-3. C120 (2 g) was obtained as a yellow powder.

The MS (m / e) of Compound C is 686. As a result of component analysis, the experimental measurement values are C: 94.38%, H: 5.57%, and the theoretical value of C ₅₄ H ₃₈ is C: 94.42%, H: It was 5.58%.

(Example 22): The synthesis method of compound C128 is demonstrated using FIG. FIG. 24 is a reaction formula for explaining a synthesis method of compound C128.

  Synthesis of intermediate C128-1: C128-1 (white solid) was synthesized by the same method as C120-3 (Example 21) except that 2-bromomethylnaphthalene was used instead of C120-2. 2.9 g) was obtained.

  Synthesis of intermediate C128-2: Synthesis was carried out in the same manner as C68-2 (Example 10) except that C128-1 was used instead of C68-1, and C128-2 (2. 69 g) was obtained.

  Synthesis of Compound C128: Compound C128 was synthesized in the same manner as C1-1 (Example 1) except that 2-perylenylboric acid and C128-2 were used instead of phenylboric acid and 2-bromothiophene. C128 (2.38 g) was obtained.

The MS (m / e) of Compound C is 530. As a result of component analysis, the experimental measurement values are C: 95.05%, H: 4.90%, and the theoretical value of C ₄₂ H ₂₆ is C: 95.06%, H: It was 4.94%.

  (Example 23): The synthesis method of compound C129 is demonstrated using FIG. FIG. 25 is a structural formula of the compound C129.

  Synthesis of Compound C129: Synthesized in the same manner as C128 (Example 22) except that 4- (2 ′, 2′-diphenylvinyl) phenylboric acid was used instead of 2-perylenylboric acid, and a yellow solid was obtained. Some C129 (1.73 g) was obtained.

The MS (m / e) of Compound C is 534. As a result of component analysis, the experimental measurement values are C: 94.35%, H: 5.60%, and the theoretical value of C ₄₂ H ₃₀ is C: 94.34%, H: It was 5.66%.

  (Example 24): The synthesis method of compound C132 is demonstrated using FIG. FIG. 26 is a reaction formula for explaining a synthesis method of compound C132.

  Synthesis of intermediate C132-1: Synthesized in the same manner as C120-1 (Example 21) except that 2-bromo-6- (bromomethyl) naphthalene was used instead of 4-diphenylboric acid. C132-1 (4.0 g) as a solid powder was obtained.

  Synthesis of intermediate 132-2: C132-2 (2.Pg), a white solid, was synthesized in the same manner as C120-2 (Example 21) except that C132-1 was used instead of C120-1. 1 g) was obtained.

  Synthesis of intermediate C132-3: Sodium cyanide (0.98 g, 0.176 mol) and N′N′-dimethylformamide (DMSO, 20 ml) were placed in a three-necked flask (100 ml) and nitrogen was added using a magnetic stirrer. Stir under atmosphere. The mixture was heated at 90 ° C. for 1 hour. A solution obtained by dissolving C132-2 (3.46 g, 0.010 mol) in DMSO (20 ml) was slowly added dropwise to the mixture so as not to exceed 160 ° C. Then, heating under reflux was continued for 1 hour. The mixture was cooled to room temperature, deionized water (50 ml) was added, and the mixture was extracted with chloroform (50 ml, twice). The organic layer was collected, washed with saturated sodium chloride (20 ml) solution, dried over sodium sulfate and filtered. The solvent was removed from the filtrate using a rotary evaporator to obtain C132-3 (1.51 g) as a white solid.

  Synthesis of Compound C132: C132-3 (2.93 g, 0.010 mol), iodine (1.27 g, 0.01 mol), and ethylene glycol diethyl ether (30 ml) were placed in a three-necked flask (100 ml). The mixture was cooled to −78 ° C. using an ethanol-liquid nitrogen bath while stirring with a magnetic stirrer. A solution of sodium methoxide (1.08 g) in methanol (20 ml) was slowly added dropwise to the mixture, and the temperature was kept at -78 ° C for 1 hour. The cooling bath was removed and the temperature was slowly raised to 0 ° C. After 4 hours at 0 ° C., the mixture was neutralized with 3% hydrochloric acid to about pH 7.0. The mixture was filtered under reduced pressure and the residue was washed with deionized water (10 ml) and dried to give C132 (2.61 g) as a pale yellow solid.

Compound C has an MS (m / e) of 582. As a result of component analysis, the experimental measurement values are C: 90.70%, H: 4.50%, N: 4.80%, and the theoretical value of C ₄₄ H ₂₆ N ₂ is C: 90.69%, H: 4.50%, N: 4.81%.

  Example 25 A method for synthesizing compound C133 will be described with reference to FIG. FIG. 27 is a reaction formula for explaining a synthesis method of compound C133.

  Synthesis of Intermediate C133-1: Anhydrous aluminum trichloride (19.8 g, 0.148 mol) and 1,2-dichloroethane (50 ml) were placed in a three-necked flask (250 ml), and a magnetic stirrer was placed under a nitrogen atmosphere. And stirred. The suspension was cooled to −10 ° C., and benzoyl chloride (14 g, 0.010 mol) was slowly added dropwise at −10 ° C. After maintaining this temperature for 1 hour, a solution of 2-bromonaphthalene (20.7 g) in 1,2-dichloroethane (100 ml) was added. The mixture was kept stirring at room temperature for 2 hours, poured into cold water (300 g) and neutralized to pH 5.0 with hydrochloric acid. The mixture was extracted with dichloromethane (50 ml, twice) and the organic layer was collected, washed with saturated sodium chloride, dried over anhydrous sodium sulfate and filtered. The solvent was removed from the filtrate using a rotary evaporator to obtain C133-1 (24.1 g) as a yellow solid.

  Synthesis of intermediate C133-2: C133 which is a white solid was synthesized in the same manner as C132-1 (Example 24) except that C133-1 was used instead of 6-bromo-2-methylnaphthalene. -2 (2 g) was obtained.

  Synthesis of Compound C133: Synthesis was carried out in the same manner as C1 (Example 1) except that C133-2 was used instead of C1-3 to obtain C133 (0.71 g) as a yellow powder.

The MS (m / e) of Compound C is 684. As a result of component analysis, the experimental measurement values are C: 94.90%, H: 5.10%, and the theoretical value of C ₅₄ H ₃₆ is C: 94.70%, H: 5.30%.

  Hereinafter, application examples in which the above-described compound is applied to OLED will be described.

  A typical OLED structure is “substrate / anode / hole transport layer (HTL) / organic light emitting layer / electron transport layer (ETL) / cathode”.

The substrate is transparent and can be attached to glass or flexible. As the flexible substrate, polyester which is one of polyimides can be used. An inorganic material can be used as the anode material. Examples of the inorganic material include metal oxides including indium oxide (ITO), zinc oxide, tin oxide, and the like, and metals having a large power function such as gold, silver, and copper. Of these, ITO is most preferable. As the material used for the anode, organic conductive polymers such as polythiophene, poly (3 ′, 4 ethylenedioxythiophene) poly (styrene sulfonic acid) (PEDOT; PSS), and polyaniline (PANI) are suitable. In general, lithium, magnesium, calcium, strontium, aluminum, indium, alloys of these with gold, silver, or copper, metal electrode layers formed by an alternating lamination method, metal with a small power function such as metal fluoride, It can be used for cathode metal. Among these, an alloy of magnesium and silver, silver, lithium fluoride, and aluminum are preferable. The triallylamine material can be used for the hole transport layer, and N, N ′-(1-methyl) naphthalene-N, N′-diphenylbenzidine (NPB) is preferably used. The electron transport layer may be, for example, tris- (8-hydroxyquinolinato) aluminum (Alq ₃ ), tris- (8-hydroxyquinolinato) gallium (Gaq ₃ ), (salicylidene-o-aminophenolate) (8-quinolinato ) A metal mixture such as gallium [Ga (Saph-q)] or a phenanthroline derivative such as 4,7-diphenyl-1,10-phenanthroline (Bphen) is used. For the organic light emitting layer, a low molecular organic material is used. At this time, a fluorescent material or phosphorescent dye is used as a dopant.

A film is formed using the compound of the present invention as a material for the organic light emitting layer. This film is used as an organic light emitting layer, and can be used as a dopant together with a host metal. At this time, it is preferable to use Alq ₃ , Gaq ₃ , and Ga (Saph-q).

  The OLED was prepared by the following method.

  (1) First, a glass substrate was washed with a detergent, deionized water, and an organic solvent on a continuous substrate. (2) Second, the hole transport material was heated to deposit a hole transport layer on the substrate. (3) Thirdly, the blue light emitting material of the present invention was heated and vapor-deposited on the hole transport layer as a light emitting layer. (4) Fourth, an electron transport layer was deposited on the light emitting layer. (5) Finally, an electron transport layer was formed by vapor deposition or sputtering of a negative electrode metal to produce a blue OLED.

  (Application Example 1) Preparation of OLED-1 to OLED3

  Preparation of OLED-1: A glass substrate coated with a conductive ITO layer was ultrasonically cleaned with a commercially available detergent and then washed with deionized water. The oil was removed from the substrate using a mixed solution of acetone and ethanol and ultrasonic waves, deionized water was removed under a clean environment, and the substrate was completely dried. And the surface treatment was performed by irradiating with a low energy cation beam.

The ITO substrate was held in a vapor deposition device. The pressure in the vaporizer was reduced to 1 * 10 ^{−5 to} 9 * 10 ⁻³ Pa. NPB was heated and deposited on the substrate as a hole transport layer at a deposition rate of 0.1 nm / s to a thickness of 55 mm. Next, Compound C55 and Alq _{3 according} to the present invention are heat-deposited, and a light emitting layer is formed on the hole transport layer so that the overall deposition rate is 0.1 nm / s and the overall thickness is 30 nm. did. At this time, the ratio of C55 to Alq ₃ was 1: 100. Further, an electron transport layer made of Alq ₃ was formed on the light emitting layer so that the deposition rate was 0.1 nm / s and the thickness was 20 nm. Finally, a cathode film that is an alloy of magnesium and silver having a thickness of 100 nm and a deposition rate of 2.0 to 3.0 nm / s on the electron transport layer, a thickness of 100 nm and a deposition rate of 0.3 nm / Each of s silver was continuously formed to prepare OLED-1.

The substrate of OLED-1 prepared by the method described above is ITO / NPB (50 nm) / BH04 (40 nm): C [x%] / Alq ₃ (20 nm) / Mg: Ag (100 nm) / Ag (100 nm). C is the light emitting material of the present invention, and x% is a doping ratio contained in C.

OLED-2 and OLED-3 have the same substrate and mixture layers as OLED-1 except for the weight of the compound C55 of the present invention doped into Alq ₃ (weight based on the total weight of the light emitting layer). . The results of these OLED-1 to OLED-3 are shown in Table 1 below, and the results are shown in FIG. FIG. 28 is an electroluminescence spectrum diagram of OLED-1 to OLED-3, where the vertical axis represents luminance and the horizontal axis represents wavelength.

  (Application Example 2): Creation of OLED-4 to OLED-6

  An issue layer was prepared in the same manner as in Application Example 1 except that C67 (Example 9) was used instead of C55. The results of OLED-4 to OLED-6 are shown in Table 2 below, and the results are shown in FIG. FIG. 29 is an electroluminescence spectrum diagram of OLED-4 to OLED-6, where the vertical axis indicates relative intensity and the horizontal axis indicates wavelength.

  (Application Example 3): Creation of OLED-7 to OLED-9

  An issue layer was prepared in the same manner as in Application Example 1 except that C82 (Example 14) was used instead of C55. The results of OLED-7 to OLED-9 are shown in Table 3 below, and the results are shown in FIG. FIG. 30 is an electroluminescence spectrum diagram of OLED-7 to OLED-9, where the vertical axis represents instantaneous efficiency and the horizontal axis represents instantaneous intensity.

  (Application Example 4): Creation of OLED-10 to OLED-12

  An issue layer was created in the same manner as Application Example 1 except that C133 (Example 25) was used instead of C55. The results of OLED-10 to OLED-12 are shown in Table 4 below, and the results are shown in FIG. FIG. 31 is an electroluminescence spectrum diagram of OLED-10 to OLED-12, where the vertical axis represents instantaneous efficiency and the horizontal axis represents instantaneous intensity.

  Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes as long as they belong to the technical scope of the present invention.

It is a reaction formula for demonstrating the synthesis method of 4-biphenyl boric acid. It is a reaction formula for demonstrating the synthesis | combining method of 6-bromo- 2-naphthaldehyde. 4 is a reaction formula for explaining a synthesis method of compound C1. 4 is a reaction formula for explaining a synthesis method of compound C12. 4 is a reaction formula for explaining a synthesis method of compound C19. 4 is a reaction formula for explaining a synthesis method of Compound C32. 4 is a reaction formula for explaining a synthesis method of compound C34. 4 is a reaction formula for explaining a synthesis method of compound C53. 1 is a structural formula showing a compound C55. 4 is a reaction formula for explaining a synthesis method of compound C60. 4 is a reaction formula for explaining a synthesis method of compound C67. 4 is a reaction formula for explaining a synthesis method of compound C68. 4 is a reaction formula for explaining a synthesis method of compound C75. 4 is a reaction formula for explaining a synthesis method of Compound C80. It is structural formula of compound C81. 4 is a reaction formula for explaining a synthesis method of compound C82. 4 is a reaction formula for explaining a synthesis method of compound C98. 4 is a reaction formula for explaining a synthesis method of Compound C101. It is a structural formula of Compound C103. It is a structural formula of Compound C107. It is a structural formula of Compound C113. It is a structural formula of Compound C116. 4 is a reaction formula for explaining a synthesis method of Compound C120. 4 is a reaction formula for explaining a synthesis method of Compound C128. It is a structural formula of Compound C129. 4 is a reaction formula for explaining a synthesis method of compound C132. 4 is a reaction formula for explaining a synthesis method of Compound C133. FIG. 4 is an electroluminescence spectrum diagram of elements OLED-1 to OLED-3. FIG. 4 is an electroluminescence spectrum diagram of elements OLED-4 to OLED-6. FIG. 6 is an electroluminescence spectrum diagram of elements OLED-7 to OLED-9. FIG. 4 is an electroluminescence spectrum diagram of elements OLED-10 to OLED-12.

Claims (7)

A compound represented by the following formula (III):

(III)

(In the formula (III), X and Y are each independently a methylene group, an aromatic 5- or 6-membered ring having 1 to 3 heteroatoms and 4 to 20 carbon atoms, and 1 to 3 carbon atoms having 1 to 3 heteroatoms. selected from the group consisting of 6-20 condensed aromatic group, and, rather than the at least one methylene group of X and Y,
Ar ₃ and Ar ₄ are each independently a hydrogen atom, a fluorine atom, a carbonyl group, a cyano group, an acyloxy group, a vinylidene group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or substituted group having 1 to 30 carbon atoms, or Unsubstituted alkoxy group, substituted or unsubstituted amino group having 2 to 30 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, carbon number 6 20 condensed aromatic group, and Ru is selected from the group consisting of arylamine group having 6 to 30 carbon atoms. ) In the formula (III), X and Y are each independently a methylene group, pyrrolyl group, thiophenyl group, furanyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyridyl group, quinolyl group, isoquinolyl group, carbazolyl group, Selected from the group consisting of phenanthridinyl group, benzothiophenyl group, benzofuranyl group, benzoimidazolyl group, benzooxazolyl group, benzothiazolyl group, oxadiazolyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, and indolyl group, and X and at least one Y is rather than a methylene group,
Ar ₃ and Ar ₄ are each independently a hydrogen atom, fluorine atom, carbonyl group, cyano group, acyloxy group, vinylidene group, methyl group, ethyl group, isopropyl group, tertiary butyl group, methoxy group, ethoxy group, isopropoxy group Tertiary butoxy group, N, N-dimethylamino group, N, N-diethylamino group, methylthio group, ethylthio group, isopropylthio group, tertiary butylthio group, phenyl group, biphenyl group, naphthyl group, anthryl group, pyrenyl group , Fluorenyl group, naphthacenyl group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) Amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, carbazolyl group p- carbazolylphenyl group, p-N, N-diphenylamino respectively from amino the group consisting of phenyl group selected compound of claim 1, wherein A compound represented by the following formula (III), wherein in formula (III), X 1 , Y ₃ , Ar ₃ and Ar ₄ are each selected from the following formulae.

(III)

A compound selected from the group consisting of the following formulas (C1) to (C141).

(C1)


(C2)


(C3)

(C4)


(C5)


(C6)


(C7)



(C8)


(C9)


(C10)


(C11)


(C12)


(C13)


(C14)


(C15)



(C16)


(C17)


(C18)


(C19)


(C20)


(C21)



(C22)


(C23)


(C24)


(C25)


(C26)


(C27)


(C28)


(C29)



(C30)


(C31)


(C32)


(C33)


(C34)


(C35)


(C36)


(C37)


(C38)


(C39)


(C40)


(C41)


(C42)


(C43)


(C44)


(C45)


(C46)


(C47)


(C48)


(C49)


(C50)


(C51)


(C52)


(C53)


(C54)


(C55)


(C56)


(C57)


(C58)



(C59)


(C60)


(C61)


(C62)


(C63)


(C64)


(C65)


(C66)


(C67)


(C68)


(C69)


(C70)


(C71)


(C72)


(C73)


(C74)


(C75)


(C76)


(C77)


(C78)


(C79)


(C80)


(C81)


(C82)


(C83)


(C84)


(C85)


(C86)


(C87)


(C88)


(C89)


(C90)


(C91)


(C92)


(C93)


(C94)


(C95)


(C96)


(C97)


(C98)


(C99)


(C100)


(C101)


(C102)


(C103)


(C104)


(C105)


(C106)


(C107)


(C108)


(C109)


(C110)


(C111)



(C112)


(C113)


(C114)


(C115)


(C116)


(C117)


(C118)


(C119)



(C120)


(C121)


(C122)



(C123)



(C124)


(C125)



(C126)



(C127)


(C128)


(C129)


(C130)



(C131)



(C132)



(C133)



(C134)



(C135)



(C136)


(C137)


(C138)


(C139)


(C140)



(C141)
The method for synthesizing a compound according to any one of claims 1 to 3 , which comprises one of the following steps a), b), c) and d).
a) The compound represented by the formula (Ia) and the formula (Ib) in the presence of an inert solvent having titanium (IV) chloride and zinc and in an inert gas atmosphere A step of reacting a compound and appropriately inserting a substituent at a required position.

(Ia)

(Ib)
(In the formula (1-a) and the formula (1-b), R _{1 to} R ₃ , R _{5 to} R ₁₀ , R _{12 to} R ₁₄ are hydrogen atoms, R ₄ is Ar ₄ —Y—, R ₁₁ is _Ar 3 is -X- .X, Y, Ar ₃ and Ar ₄ are as defined in each of any one of claims 1-3.)

b) an inert solvent presence with zinc and titanium tetrachloride (IV), in an inert gas atmosphere, in the formula ( 'compound of formula represented by) (I-b' I- a) Table And a step of appropriately inserting a substituent at a required place.

(Ia ')

(Ib ′)
(In formula (Ia ′) and formula (Ib ′), R _{1 to} R ₃ , R _{5 to} R ₁₀ , R _{12 to} R ₁₆ are hydrogen atoms, and R ₄ is Ar ₄ —Y—. _{There, R 11} is .X is _{Ar 3} -X-, Y, _Ar 3 and Ar ₄ are as defined in each of any one of claims 1-3.)

c) From the structural formula (Ia), the structural formula (Ia ′), the structural formula (Ib), and the structural formula (Ib ′) in the presence of an inert solvent having an alkali. A step of reacting one of the compounds selected from the group and the compound represented by the structural formula (Ic), and inserting a substituent appropriately at a required position.

(Ic)
(In the formula _{(I-c), R 1} ~R 3, R 5 ~R 7 is a hydrogen atom, _{R 4} is _Ar 4 -Y-, either Y and Ar ₄ each claim 1-3 Or R ₁₇ is a linear or branched alkyl group having 1 to 6 carbon atoms.)

d) an inert solvent presence with the alcoholate and iodine alkali metal or alkaline earth metal, and a compound represented by the structural formula (the compound represented by I-d) and structural formula (I-e) The process of making it react and inserting a substituent into a required place suitably.

(Id)

(Ie)
_{(Wherein, R 8 ~R 10, R 12} ~R 14 is a hydrogen _{atom, R 11} is _Ar 3 -X-, defined in any one of the respective X and Ar ₃ claims 1-3 it is one that is.) A thin film useful for organic electroluminescent diodes,
The said thin film made from the compound as described in any one of Claims 1-4 , and vapor-deposited on the board | substrate. An organic electroluminescence diode comprising the thin film according to claim 6 .